Fungicidal compound of the aminophenyl diazo series



United States Patent s flaims. c1. ate-326.5

The present invention relates to and has as its objects new and useful fungicidal compositions and methods of combating fungi therewith. Generally the active compounds of the new compositions may be represented by the following formulae of which according to the latest literature the second formula is preferred. In these formulae R and R denote hydrogen and/or eventually substituted aliphatic,

araliphatic or aromatic radicals; R and R may also include the nitrogen or other hetero atoms to form a ring; R stands for an eventual substituent of the benzene nucleus such as alkyl, halogen, nitro, carboxy and the like; R and R stand for the cyano group and/ or the groups COR COR R and R denote organic radicals which may be bonded with the -CO group directly or via hetero atoms such as nitrogen or oxygen. Moreover, they may form a cyclic B-diketone together with the --CH- group or represent the radical of a heterocyclic ring such as the pyrazolone ring which contains a reactive methylene group on account of appropriate substitution.

As it is to be seen these formulae differ from each other only by the position of the double bond, but it is 3,15%,151 Patented Sept. 22, 1964 ice without importance for the present invention in which state the compounds of this invention are existing.

It is known that p-aminophenyl-hydrazine compounds are especially effective against micro organisms living in agricultural soil and causing germ diseases. 0n the other hand, their efiect on leaf fungi is negligible. Aminophenyldiazo compounds such as dimethyl-aminophenyldiazo sulfonate show the same effects.

Surprisingly it has now been found that the above class of substances related to these groups of compounds is also highly effective against fungus infections of the green parts of plants. These classes of substances as it is to be seen above are coupling products obtainable from basically substituted aromatic diazonium salts and compounds containing reactive methylene groups. They may be considered either as azo compounds or also as bydrazones.

As suitable coupling components in the meaning of this invention there may be mentioned the following: cyanacetic ester, malonic acid ester, acetoacetic ester, acetoacetic acid amides, acetylacetone, dihydron'esorcinol, pyrazolone and the like. The production of the substances some of which are new is effected by methods known as such and is described in the following example which is given for the purpose of illustrating the invention.

The compound thus obtained in a yield of about can be re-dissolved from methanol forming red-brown brilliant crystals which melt at 123 C.

In a similar way there may be obtained the following compounds as well as others falling within the scope of this application.

CH 0 0 O CzHs NCtH4NHN=C Redbrown crystals from methanol 113.

CH 0 0 CH N-CBH4NHN=C Dark red leaflets from methanol decomposition.

CH ON CH3 0 O C0115 N C H4NHN=C Brown crystals from methanol 85.

CH 6 O 0 O H5 CH3 0 0N 0a NCsHi-NH-N=C Red-brown crystals from alcohol..

CH 0 0 0 Ca Table Z--Continued R X R; M.]?

CH; C O CH;

N C@H4-NH N =0 Dark red crystal from alcohol 127. c a C O N H@ CH; C 0 CH NCH4NHN=O Red crystals from alcohol 143. CE; 0 ON H CH C OCH NCaH4NHN=O CH; Red-brown crystals from acetic ester 176 decomposition. CH 0 0-0fi,

CH3 0 OOH;

NC H4NH-N=O CH-C O OH Darl: red crystals from dimethyliorma- 252 decomposition. CH3 0 OCH2 nude CH O ONH N-CoH4NHN=C Dark violet crystals from alcohol 209 decomposition. 0H3 0=N CH C O NCaH5 NCs 4-NHN=C Red crystals from methanol 142 decomposition. C V v C:

Crystals from methanol Dark red crystals from dimethyl-formamide.

Red crystals from petroleum-ether Red crystals from methanol Red crystals from alcohol Red crystals from alcohol Dark red crystals from alcohol Red brown crystals from alcohol Dark red crystals from light petrol 252 decomposition.

Table 1-Continued R X B Ml GE -H2 C 0 0E3 N- -NH-N=C Red crystals from acetic acid ester 112. CHgr-G: c 0 CH GHQ-CH2 C 0 CH N NH-N=O Light-brown crystals from methanol ISO/182. CHr-Gfifl F c 0 CH3 C O OH CH -CI-I C O C H; Cfiz N{ NHN=C Brown crystals from methanol /111.

cHz0l 0 0 CH: CH CH -CH COCH;

N-NHN=C Red crystals from light petrol 97. CHr-CHC COCH CH- CH C 0 CH 0 N-NHN= 0 Red crystals from methanol 170.

OHFOHE C 0 CH GET-0H2 C 0 CH3 S NNHN=C Brown needles from alcohol GH Cfiz C O CH;

CH CH C 0 C H;

N -NHN= 0 Red leaflets from methanol 94/96". Cfircz o 0 CH GE -CH C 0 CH N- -NHN=N=C Red needles from methanol /141". CIIy-Cfil o 0 CH CH C 0 CH N-NHH=C Orange crystals from dimethylformamiden 242%? decomposi- C H; I C O C H3 0 O CH C 0 CHa C H CH N-NHN=C' Orange crystals from light petrol.-. 90.

( 3H C 0 CH2 CH Gila-( 3 C 0 CH3 N NHN=C Dark red crystals from methanol 58/60". o Hz-C 0 0 CH3 C 0 CH5 11o CH CHr-N -NHN=C Red crystals from methanol 151 311 C 0 CH;

C 0 CH ClCH CI-IrNNHN=C Dark red crystals from acetic ester. 128/129".

CH; C 0 CH;

C Bi -CH C OCH;

N-CH -CH;;NNHN=O Red crystals from methanol 239 decomposition. CHa-Cz CH; C 001-1 CH (1H2 Red crystals from light petrol 7 Table ]Continued R X B M.P

' /C 0 CH3 CH NHNHN=G\ Yellow-brown crystals from methanol 52.

C O 0 Ha OH;

O O C H; NH-N=C Brown1 clrystals from dimethyl-iormamide/ 183". a c0 0 C O C H3 /0 0011 (CHgCHgCHzCH!) ;N NHN=O Brownish red crystals from methanol 63/64.

O OCH:

Part of these compounds also may be obtained by the reaction of corresponding p-amino-phenylhydrazines and corresponding triketo-compounds.

The fungicidal compounds according to the invention are highly active leaf fungicides. Their eifect is shown in the following Table 2 taking Phylophthora infestans on tomatoes as an example without thereby limiting the effect of the compounds to the said disease. The com- Effect on phytophthora on tomatoes in a concentration R X R1 (aqueous) oi 0 H 0 O 0 H NNHN=C 0 0 o 0 4 2 C C 0 CH3 CH3 C 0 CH3 N C 5H NH-N=C 11 32 Ca 0ONH 0 H3 C O- C Hz N-C eH4NHN=C C H: 44 49 76 C a C O C fin CH3 C ONH NCsH4NH-N=C 29 31 C 3 C=N CH C 0 CH3 N NHN=C 0 0 0 C 0 CH3 HEN-- C aH4NH-N=C 17 18 39 54 68 o O CHa C 2H5 C O C H N C aH4--NH'N= C 2 25 53 02 15 C 0 CH GHQ-CH O 0 CH NCsH1-NHN=G 1 9 28 C Hg-C Hg C O C H CH3 G O O 01H:

NCoH4-NHN=G 0 0 2 3 9 C 2 C O CH;

Table 2Continued Efiect on phytophthora on tomatoes in a concentration (aqueous) of- R X It;

CH3 COOCzHs NCBH4NHN:O 3 13 40 54 CH3 ON 1 CH COCGHS N-C HlNH-N=C 3 8 I 21 36 1. CH3 COOCzHs Zinc-ethylene-bisdithiocarbamate 10 22 32 54 57 From Tables 3 to 5 there can be seen the results of with other extenders or in the form of solutions, emulexperiments with 3 compounds taken as examples for the sions or suspensionsor also in the solid form as a granusuitability of the class of compounds to be used according 29 late either alone or in combination with other plant proto the invention as agents for treating seeds and soil tectives, fertilizers or agents for improving the soil strucagainst fungus diseases. ture.

The experiments have been carried out in usual manner. For the disinfecting and soil treatment experiments The preparations were extended with talcum and used as there were used as seed peas which are susceptible to dry disinfectants at the concentrations in active subdiseases and were sown into compost soil naturally instance and in the quantities indicated. It is of course tested by Pythiam ultimum in ratio of 2 x 50 grains also possible to use other powdered extenders or to preper test member. After a test duration of 3 weeks at pare genuine solutions, emulsions or suspensions to be temperatures of about 18 C., the results were evaluated used for treating seeds. For soil treatment, the preparaby counting the healthy plants which had grown out of tions are milled with talcum in a proportion of about 100 seeds in each case. The mean effect is illustrated 1:10 and then further extended with line sand. Here also in each case by the increase in the number of healthy it is of course possible to apply the preparations together plants compared with the untreated control member.

Table 3 Disinfection test, pythium Soil treatment test, pythitnn Preparation Healthy Healthy Cone, Quantity plants, Cone. of active plants, percent gJkg. percent subst. in soil percent 3 weeks in ppm. 3 weeks after sowing alter sowing Untreated 12 12 Phenyl-Hg-acetate 2. 2 Hg 2 40 100 Hg 37 2 77 15 (0H3) 2N N=N-0H (C O-CH 2 7e 38 2 s3 51 Table 4 Disinfection test, pythium Soil treatment test, pythium Preparation Healthy Healthy Cone, Quantit plants, Cone. of active plants, percent gJkg. percent subst. in soil percent 3 weeks in ppm. 3 Weeks after sowing after sowing Untreated 14 0 w Plienyl-llg-acetatenu 28 16 OO-CH2 2 s4 23 (CH3)2N NH-N=OH 011-0 0 on 2 s4 61 2 79 so i (IO-CH2 Table 5 Disinfection test, pythium Soil treatment test, pythium Preparation Healthy Healthy Cone, Quant'ty plants, Cone. of active plants, percent gJkg. percent subst. in soil percent 3 weeks in ppm. 3 weeks after sowing after sowing Untreated Q Phenyl-Hg-aeetate 00 Hg 13 I 9s 2i NH2 N=N-CH(COCH3)11 flfl 43 66 sno 83 1 1 The effect of some representatives of the class of substances according to the invention on Phytophthora infestans is particularly noteworthy, results being achieved which have hitherto not been obtainable with any known fungicide.

The compounds according to the invention are distin-' 11,0 (JO-Q N--NHN=O V H C o -0 02H, 3. The compound of the following formula H O GEN NNHN=O 1130 o 0-0 02m 4. The compound of the following formula n O 0 on,

5. A p-amino-phenyl-hydrazine of the formula:

- in which A stands for a member selected from the group consisting of amino, dimethyl-amino, diethyl-amino, and pyrrolidyl I; R is a member selected from the group consisting of hydrogen, lower alkyl, chlorine and carboxyl; B and D each stand for a member selected from the group 7 consisting of lower alkyl carbonyl, lower alkoxy-carbonyl,

cyano, phenyl carbonyl, nitrophenyl carbonyl, phenyl amino carbonyl, chlorophenylamino carbonyl, B and D together with the carbon atom to which they are attached form a member selected from the group consisting of CO-OHz and and

CHCOOH CONH 6. A compound of the formula References Cited in the file of this patent UNITED STATES PATENTS Bonrath Sept. 15, 1936 Goldberg et al. Nov. 10, 1953 Dunlop et a1 June 15, 1954 Urbschat'et al. Nov. 3, 1959 Lutz et al. Dec. 8, 1959 McCall et al. Jan. 31, 1961 

4. THE COMPOUND OF THE FOLLOWING FORMULA
 5. A P-AMINO-PHENYLL-HYDRAZINE OF THE FORMULA: 